The principle of obtaining amines starting from an olefin, hydrogen, carbon monoxide and a primary or secondary amine is known. Various techniques embodying this principle have been described using catalysts of various kinds.
Early work in this field taught that aliphatic acids may be obtained by reacting carbon monoxide with an olefin and steam and that ammonia may be reacted with carbon monoxide to produce formamide. U.S. Pat. No. 2,422,632 (1944) appears to be the first work to suggest a process by which an olefin may be reacted with carbon monoxide and ammonia or an amine having replaceable hydrogen to form an amide or amine.
U.S. Pat. No. 2,497,310 (1946) defined a process for the synthesis of aliphatic amines which consisted of introducing carbon monoxide, hydrogen, a compound from the group consisting of ammonia and amines having at least one hydrogen attached to amino nitrogen, an unsaturated compound containing a non-benzenoid double bond between carbon atoms, and a catalytic quantity of cobalt metal, into a pressure resistant vessel and heating the resultant mixture within the range of 50.degree.-350.degree. C. under a reaction pressure in excess of 50 atm, whereby a reaction product containing amines is produced and thereafter separated from the reaction product produced.
In Shell International Research Maatschappy B. V. Neth. Appl. 6,405,802 Nov. 30, 1964; corresponding to U.S. Pat. No. 3,234,283 (1966), tertiary amines are obtained in improved yields and at lower pressures than in prior processes by treating CO, hydrogen and a secondary amine with a C.sub.10 -C.sub.13 olefinic mixture in the presence of a cobalt carbonyl-tri alkylphosphine catalyst.
U.S. Pat. No. 3,513,200 (1970) covers the utilization of Group VIII metal complexes bearing a biphyllic ligand such as a phosphine and, optionally these complexes may contain a metal hydride complexed with CO. There can be added, as an adjuvant, poly(heterocyclo)amines. The reaction is realized at a temperature between 50.degree. and 200.degree. C. and under a pressure ranging from 5 to 300 atmospheres. A significant proportion of aldehydes is obtained and the selectivity to amines is still in this case only very moderate.
In a paper by Iqbal published in Helvetica Chemica Acta, Volume 54, pages 1440 to 1445 (1971), as well as in U.S. Pat. No. 3,947,458 (1976), the catalytic aminomethylation of olefins is described employing a rhodium oxide catalyst, an iron carbonyl catalyst and a mixed rhodium oxide/iron carbonyl catalyst.
U.S. Pat. No. 4,096,150 (1978) discloses a process for the manufacture of tertiary amines wherein an olefin, hydrogen, CO and secondary amine are reacted in the presence of a coordination complex catalyst of a Group VIII metal and a ligand, the donor atom of which is oxygen, nitrogen or sulfur.
In J. Org. Chem. 45 3370 (1980), Laine, et al. describe the results of their studies on the aminomethylation reaction using a variety of Group VIII transition-metal carbonyl catalyst precursors.
U.S. Pat. No. 4,292,242, by Laine, states that the object of its invention is to provide improved methods of aminomethylation which are more selective and lead to fewer unwanted by-products such as alcohols and carboxy amides. A further object mentioned was to provide a more stable mixed carbonyl catalyst, the use of which would result in higher yields of the desired amines. Here the claimed catalyst is a mixed ruthenium carbonyl/iron carbonyl in a suitable solvent. Again, this process leads to a formamide by-product.
In J. Org. Chem., 47, 445 (1982), Jachimowicz, et al. discuss the various approaches which have been used to attempt to devise a one-step, efficient and general conversion of olefins to amines. Among the catalysts used in processes devised by various people have been iron pentacarbonyl, rhodium oxide, ruthenium/iron carbonyl and iridium catalysts. The discussion in this article examines the feasibility of various aminomethylation syntheses.
In the processes discussed above, the selective production of a polymeric tertiary amine is not contemplated.
In U.S. Pat. No. 4,297,481, Jachimowicz discloses a process for forming a polymeric polyamine/amide wherein said amino/amido nitrogens are positioned in the polymer backbone by contacting a monomeric nitrogen compound which has at least two labile hydrogens bonded to the nitrogen atoms therein, a monomeric hydrocarbon compound containing at least two olefinic groups therein, carbon monoxide and water in the presence of a catalytic amount of a rhodium-containing compound. This invention describes the use of ammonia or primary amines. The preparation of polymers with pendant amine and amide groups is described in U.S. Pat. No. 4,312,965. These polymers are prepared from polymeric polyolefins, carbon monoxide, and monomeric nitrogen compounds as described previously. Again, rhodium or a rhodium-containing compound serves as catalyst. Isolation of the product polymer is by precipitation with water from an organic solvent.
In prior processes in the art by which aminomethylation takes place, the reaction must often take place at high temperatures and/or pressures, the olefin conversion and selectivity to the desired tertiary amines is not as high as desired, and unwanted by-products are often formed. Additionally separation of the product polymer is by means such as precipitation which do not allow easy catalyst recycle.
It would be a considerable advance in the art to devise a system for selectively producing tertiary polymeric amines from CO, hydrogen, polymeric olefins and secondary amines by an aminomethylation process which results in a product with a high percentage of polymeric tertiary amines. The resulting polymeric amines are useful as surfactants, wet strength agents and flocculating agents. In such applications the polymeric products are desirable and, as stated, it would be a considerable advance to provide them in substantial yield. In addition, it would be an advance over prior art to devise a process with good selectivity which proceeds under mild reaction conditions, without undesired side reactions and affords easy and efficient separation of the desired product, free of catalyst.